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Literature summary for 4.2.3.171 extracted from

  • Rabe, P.; Janusko, A.; Goldfuss, B.; Dickschat, J.S.
    Experimental and theoretical studies on corvol ether biosynthesis (2016), Chembiochem, 17, 146-149.
    View publication on PubMed
Search for more literature for 4.2.3.171

Organism

Organism UniProt Comment Textmining
Kitasatospora setae E4N7E5
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Kitasatospora setae DSM 43861 E4N7E5
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Substrates and Products (Substrate)

Substrates Comment Substrates Organism Products Comment (Products) Rev. Reac.
(2E,6E)-farnesyl diphosphate + H2O no activity with geranylgeranyl diphosphate. The enzyme forms (+)-corvol ether B and (+)-corvol ether A in the ratio of 3:1. Quantum chemical calculations reveal that a sequence of two 1,2-hydride migrations in the cyclisation cascade from (2E,6E)-farnesyl diphosphate to the corvol ethers A and B are energetically more favourable than an alternative pathway through one 1,3-hydride shift. Because these calculations do not give any insights into what extent the relevant intermediate cations in the two hypothetical cyclisation reactions might be stabilised by the terpene cyclase, isotopic labelling experiments are performed. These pointed to the same enzyme mechanism, thus giving evidence for a cyclisation mechanism through two 1,2-hydride shifts Kitasatospora setae (+)-corvol ether A + diphosphate (+)-corvol ether B i.e. (1R*,4S*,4aR*,7R*,8aR*)-4,7-dimethyl-1-(propan-2-yl)decahydro-1,7-epoxynaphthalene ?
(2E,6E)-farnesyl diphosphate + H2O no activity with geranylgeranyl diphosphate. The enzyme forms (+)-corvol ether B and (+)-corvol ether A in the ratio of 3:1. Quantum chemical calculations reveal that a sequence of two 1,2-hydride migrations in the cyclisation cascade from (2E,6E)-farnesyl diphosphate to the corvol ethers A and B are energetically more favourable than an alternative pathway through one 1,3-hydride shift. Because these calculations do not give any insights into what extent the relevant intermediate cations in the two hypothetical cyclisation reactions might be stabilised by the terpene cyclase, isotopic labelling experiments are performed. These pointed to the same enzyme mechanism, thus giving evidence for a cyclisation mechanism through two 1,2-hydride shifts Kitasatospora setae DSM 43861 (+)-corvol ether A + diphosphate (+)-corvol ether B i.e. (1R*,4S*,4aR*,7R*,8aR*)-4,7-dimethyl-1-(propan-2-yl)decahydro-1,7-epoxynaphthalene ?
additional information incubation of the purified enzyme with geranyl diposphate yields small amounts of several acyclic and cyclic monoterpenes, with linalool as the main product Kitasatospora setae ?
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additional information incubation of the purified enzyme with geranyl diposphate yields small amounts of several acyclic and cyclic monoterpenes, with linalool as the main product Kitasatospora setae DSM 43861 ?
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 ?